Surface-enhanced Raman spectroscopy stu tudy of f commercial fr - - PowerPoint PPT Presentation

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Surface-enhanced Raman spectroscopy stu tudy of f commercial fr - - PowerPoint PPT Presentation

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Surface-enhanced Raman spectroscopy stu tudy of f commercial fr fruit ju juic ices Carlo Camerlingo 1 , Marianna Portaccio 2 , Rosarita Tat 3 , Maria Lepore 2 , Ines Delfino 4,* 1 CNR-SPIN, Consiglio Nazionale delle Ricerche, Institute for

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Surface-enhanced Raman spectroscopy stu tudy

  • f

f commercial fr fruit ju juic ices

Carlo Camerlingo1, Marianna Portaccio2, Rosarita Taté3, Maria Lepore2, Ines Delfino4,*

1CNR-SPIN, Consiglio Nazionale delle Ricerche, Institute for superconductivity,

innovative materials and devices, Pozzuoli, Italy.

  • 2Dip. Medicina Sperimentale, Seconda Università di Napoli, Napoli, Italy.

3Institute of Genetics and Biophysics – ABT, Naples, Italy.

  • 4Dip. Scienze Ecologiche e Biologiche, Università della Tuscia, Viterbo, Italy.

*Correspondence:delfino@unitus.it; Tel.: +39-0761-357-026

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Characterization of fruit juice and pulp by SERS spectroscopy using visible light (l = 632.8 nm) and a micro-Raman spectroscopy setup Surface enhanced Raman Spectroscopy (SERS) using a home-made Gold nanoparticle-based substrate. Numerical background subtraction by wavelet based algorithm. Evaluation of juice and pulp contents (glucose, fructose and pectin and so on) Contamination or degradation processes Territorial characterization

Surface-enhanced Raman spectroscopy study of commercial fruit juices

  • C. Camerlingo, M. Portaccio, R. Tatè, M. Lepore, I. Delfino

Fruit juice and pulp characterization by SERS Spectroscopy ____

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Micro-Raman Spectroscopy_____________________

Spectral analysis methods are FAST, NONINVASIVE and usually INEXPENSIVE: They are particularly suitable for food characterization and food process monitoring and food quality evaluation (also in situ and online).

LASER SAMPLE

Surface-enhanced Raman spectroscopy study of commercial fruit juices

  • C. Camerlingo, M. Portaccio, R. Tatè, M. Lepore, I. Delfino
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______SERS_____________Surface Enhanced Raman Spectroscopy

high local enhancements of the electromagnetic energy (large enhancement of Raman signal) LIGHT NANOSCALE METALS collective oscillations of conduction electrons: LOCALIZED SURFACE PLASMON RESONANCES

Electromagnetic interaction

Surface-enhanced Raman spectroscopy study of commercial fruit juices

  • C. Camerlingo, M. Portaccio, R. Tatè, M. Lepore, I. Delfino
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  • I. Delfino, M. Lepore, R. Taté, M. Portaccio, Int. Electronic Conference on Sensors and Applications

2014 (www.mdpi.com/journal/sensors/)

0.01% HAuCl4 solution + 1% sodium citrate

Au nanoparticles (GNPs): Fabrication process______

Turkevich and Frens method: the reducing agent (sodium citrate) acts as stabilizing agent by adsorbing onto the metal surface and avoiding nanoparticle aggregation through electrostatic repulsions.

Surface-enhanced Raman spectroscopy study of commercial fruit juices

  • C. Camerlingo, M. Portaccio, R. Tatè, M. Lepore, I. Delfino
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Estimated GNP Size by Absorption A: 20±2 nm B: 47±5 nm Estimated GNP Size by TEM and DLS A: 18±10 nm B: 47±13 nm (greater dispersion)

TEM images; size bar 100 nm

GNPs of different sizes can be obtained, depending on the amount of sodium citrate. They were characterized by using DLS, TEM and absorption spectroscopy

B and A GNP preparations l (nm) d (nm)

Position of the Plasmon Resonance peak as a function of the particle diameter for GNPs in water.

Surface-enhanced Raman spectroscopy study of commercial fruit juices

  • C. Camerlingo, M. Portaccio, R. Tatè, M. Lepore, I. Delfino
  • W. Haiss et al, Anal. Chem. 79 (2007)

4215.

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Surface-enhanced Raman spectroscopy study of commercial fruit juices

  • C. Camerlingo, M. Portaccio, R. Tatè, M. Lepore, I. Delfino

GNP preparation based SERS Substrates_______

Raman signal from GNP based substrates

Line 1: GNP A preparation Line 2: GNP B preparation

NO SPECIFIC FEATURES

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IDWT DWT

  • C. Camerlingo et al, Meas. Sci. Technol. 17 (2006) 298.

Numerical Data treatment based on wavelet algorithm_______

Surface-enhanced Raman spectroscopy study of commercial fruit juices

  • C. Camerlingo, M. Portaccio, R. Tatè, M. Lepore, I. Delfino
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(c) (b) (a) Raman signal (arb. units) wavenumber shift (cm

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Raman spectra of clear apple juice (data not treated) for bare juice drop (a), juice drop on A- preparation based substrate and for (b) juice drop on B-preparation based substrate (c).

The spectra are arbitrarily shifted along the y-axis.

When B-preparation GNP based substrates is used Raman features are observed  SERS By using this substrate SERS spectra are detected also for commercial pulp (NO GNP based substrate = undetectable Raman signal)

Surface-enhanced Raman spectroscopy study of commercial fruit juices

  • C. Camerlingo, M. Portaccio, R. Tatè, M. Lepore, I. Delfino

Raman and SERS spectra of apple juice _______

Juice on GNP B-preparation substrates Juice on GNP B-preparation substrates Juice on bare glass slide (no GNP)

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Apple/pear

Raman signal (arb. units) wavenumber shift (cm

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Apple juice Apple/pear pulp

400 500 600 700 200 400 600 800 1000 Raman signal (arb. units) wavenumber shift (cm

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Deconvolution in Lorentzian functions of SERS spectrum in the range 350-700 cm-1 of clear apple juice on B-preparation based substrate. Red line is the convolution of the peaks

  • found. Black peaks are assigned to fructose (peaks at 417, 475, 512, 591, 624 cm-1) , while
  • range ones refer to pectin (539, 679 cm-1) .

Surface-enhanced Raman spectroscopy study of commercial fruit juices

  • C. Camerlingo, M. Portaccio, R. Tatè, M. Lepore, I. Delfino

SERS spectra of apple juice and pulp (low frequency range)__

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Deconvolution of Raman (SERS) spectrum of apple juice. An attempt of assignment of Raman modes for the main components of the apple juice is indicated. The strong peak at about 1600 cm-1 is presumably generated by residual fiber content (lignite).

Surface-enhanced Raman spectroscopy study of commercial fruit juices

  • C. Camerlingo, M. Portaccio, R. Tatè, M. Lepore, I. Delfino

SERS spectrum of apple juice (high frequency range)_______

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Deconvolution of SERS spectrum of apple/pear smashed pulp. An attempt of assignment of Raman modes for the main components is indicated.

Surface-enhanced Raman spectroscopy study of commercial fruit juices

  • C. Camerlingo, M. Portaccio, R. Tatè, M. Lepore, I. Delfino

SERS spectrum of apple/pear smashed pulp (high frequency range)________

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Table taken from C. Camerlingo, F. Zenone, I. Delfino, N. Diano, D.G. Mita, M. Lepore, Investigation on clarified fruit juice composition by using visible light micro-Raman spectroscopy, Sensors 7 (2007) 2049-2061.

  • 20. Cerchiaro, et al Carbohydrates Research 2005, 340, 2352-2359.
  • 21. Engelsen, S.B.; Noorgard L. Carbohydrates Polimers 1996, 30,9-24.
  • 23. Koyama, Y. et al. J. Raman Spectrosc. 1988, 19, 37-49.

Tentative assignment of main Raman modes found in apple juice spectra

Surface-enhanced Raman spectroscopy study of commercial fruit juices

  • C. Camerlingo, M. Portaccio, R. Tatè, M. Lepore, I. Delfino
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 The realized home-made GNP based substrate has enabled to obtain clear Raman spectra of commercial apple juice and pear/apple smashed pulp, that feature a low Raman signal.  The detected good SERS spectra enabled to evidence the presence of fructose and pectin in the untreated samples.  The overall inspection of the results has confirmed the potentialities of SERS in food industry especially for the eventual on-line product evaluation.

Surface-enhanced Raman spectroscopy study of commercial fruit juices

  • C. Camerlingo, M. Portaccio, R. Tatè, M. Lepore, I. Delfino

____________Summary___________